\emph{Ab initio} study of (100) diamond surface spins

Unpaired electronic spins at diamond surfaces are ubiquitous and can lead to excess magnetic noise. They have been observed in several studies to date, but their exact chemical nature is still unknown. We propose a simple model to explain the existence and chemical stability of surface spins associated with the $sp^3$ dangling bond on the (100) diamond surface using density functional theory. We find that the (111) facet, which is naturally generated at a step edge of (100) crystalline diamond surface, can sterically protect a spinful defect. Our study reveals a mechanism for annihilation of these surface spins upon annealing, consistent with recent experimental results. We also demonstrate that the Fermi-contact term in the hyperfine coupling is not negligible between the surface spins and the surrounding nuclear spins, and thus \textit{ab initio} simulation can be used to devise a sensing protocol where the surface spins act as reporter spins to sense nuclear spins on the surface.Comment: 11 figure

Electrically driven optical interferometry with spins in silicon carbide

Interfacing solid-state defect electron spins to other quantum systems is an ongoing challenge. The ground-state spin's weak coupling to its environment bestows excellent coherence properties, but also limits desired drive fields. The excited-state orbitals of these electrons, however, can exhibit stronger coupling to phononic and electric fields. Here, we demonstrate electrically driven coherent quantum interference in the optical transition of single, basally oriented divacancies in commercially available 4H silicon carbide. By applying microwave frequency electric fields, we coherently drive the divacancy's excited-state orbitals and induce Landau-Zener-Stuckelberg interference fringes in the resonant optical absorption spectrum. Additionally, we find remarkably coherent optical and spin subsystems enabled by the basal divacancy's symmetry. These properties establish divacancies as strong candidates for quantum communication and hybrid system applications, where simultaneous control over optical and spin degrees of freedom is paramount.Comment: 17 pages, 4 figure

High-fidelity spin and optical control of single silicon-vacancy centres in silicon carbide

Scalable quantum networking requires quantum systems with quantum processing capabilities. Solid state spin systems with reliable spin–optical interfaces are a leading hardware in this regard. However, available systems suffer from large electron–phonon interaction or fast spin dephasing. Here, we demonstrate that the negatively charged silicon-vacancy centre in silicon carbide is immune to both drawbacks. Thanks to its 4A2 symmetry in ground and excited states, optical resonances are stable with near-Fourier-transform-limited linewidths, allowing exploitation of the spin selectivity of the optical transitions. In combination with millisecond-long spin coherence times originating from the high-purity crystal, we demonstrate high-fidelity optical initialization and coherent spin control, which we exploit to show coherent coupling to single nuclear spins with ∼1 kHz resolution. The summary of our findings makes this defect a prime candidate for realising memory-assisted quantum network applications using semiconductor-based spin-to-photon interfaces and coherently coupled nuclear spins

BLUF Domain Function Does Not Require a Metastable Radical Intermediate State

BLUF (blue light using flavin) domain proteins are an important family of blue light-sensing proteins which control a wide variety of functions in cells. The primary light-activated step in the BLUF domain is not yet established. A number of experimental and theoretical studies points to a role for photoinduced electron transfer (PET) between a highly conserved tyrosine and the flavin chromophore to form a radical intermediate state. Here we investigate the role of PET in three different BLUF proteins, using ultrafast broadband transient infrared spectroscopy. We characterize and identify infrared active marker modes for excited and ground state species and use them to record photochemical dynamics in the proteins. We also generate mutants which unambiguously show PET and, through isotope labeling of the protein and the chromophore, are able to assign modes characteristic of both flavin and protein radical states. We find that these radical intermediates are not observed in two of the three BLUF domains studied, casting doubt on the importance of the formation of a population of radical intermediates in the BLUF photocycle. Further, unnatural amino acid mutagenesis is used to replace the conserved tyrosine with fluorotyrosines, thus modifying the driving force for the proposed electron transfer reaction; the rate changes observed are also not consistent with a PET mechanism. Thus, while intermediates of PET reactions can be observed in BLUF proteins they are not correlated with photoactivity, suggesting that radical intermediates are not central to their operation. Alternative nonradical pathways including a keto–enol tautomerization induced by electronic excitation of the flavin ring are considered

Sources of Variation in Physician Adherence with Clinical Guidelines: Results from a Factorial Experiment

BACKGROUND: Health services research has documented the magnitude of health care variations. Few studies focus on provider level sources of variation in clinical decision making-for example, which primary care providers are likely to follow clinical guidelines, with which types of patient. OBJECTIVES: To estimate: (1) the extent of primary care provider adherence to practice guidelines and the unconfounded influence of (2) patient attributes and (3) physician characteristics on adherence with clinical practice guidelines. DESIGN: In a factorial experiment, primary care providers were shown clinically authentic video vignettes with actors portrayed different “patients” with identical signs of coronary heart disease (CHD). Different types of providers were asked how they would manage the different “patients” with identical CHD symptoms. Measures were taken to protect external validity. RESULTS: Adherence to some guidelines is high (over 50% of physicians would follow a third of the recommended actions), yet there is low adherence to many of them (less than 20% would follow another third). Female patients are less likely than males to receive 4 of 5 types of physical examination (p < .03); older patients are less likely to be advised to stop smoking (p < .03). Race and SES of patients had no effect on provider adherence to guidelines. A physicians’ level of experience (age) appears to be important with certain patients. CONCLUSIONS: Physician adherence with guidelines varies with different types of “patient” and with the length of clinical experience. With this evidence it is possible to appropriately target interventions to reduce health care variations by improving physician adherence with clinical guidelines